The effects of epimerization at the 3(1)-position of bacteriochlorophylls c on their aggregation in chlorosomes of green sulfur bacteria. Control of the ratio of 3(1) epimers by light intensity

R- and S-epimerization at the 3(1) position of bacteriochlorophyll (BChl) c and the formation of rod-like aggregates in chlorosomes of green sulfur bacteria were markedly affected in Chlorobium (Cb.) tepidum and Cb. limicola by cultivation under various light intensities (photon fluence rate). The stronger the light, the higher the ratio of the S-epimer to the R-epimer for each homolog of BChl c in the bacteria. S[P,E] BChl cF and S[I,E] BChl cF were found to be the major S-epimers in Cb. tepidum and Cb. limicola, respectively. R[P,E] BChl cF decreased markedly compared to R[E,E] BChl cF in Cb. tepidum, whereas no observable change in the ratio of R[P,E]/R[E,E] was detected for Cb. limicola. With increase in light intensity the Qy absorption maximum of the bacteria shifted to shorter wavelengths. In vitro spectroscopic studies of the aggregates showed a marked difference in the formation of aggregates from R- and S-epimers of BChl c; the S-epimers formed aggregates much more slowly than did the R-epimers. These results suggest that the ratio of the epimers of BChl c might significantly affect the aggregation of BChl in the chlorosome. We propose different roles for the R- and S-epimers in chlorosomes of Cb. limicola and Cb. tepidum.     

Labdane diterpenes from the rhizomes of Hedychium coronarium

A new labdane diterpenoid, (E)-labda-8(17),12-dien-15,16-olide (1) together with eight known compounds, coronarin D (2), coronarin D methyl ether (3), coronarin D ethyl ether (4), isocoronarin D (5), coronarin B (6), labda-8(17),11,13-trien-15,16-olide (7), (E)-labda-8(17),12-diene-15,16-dial (8) and 16-hydroxylabda-8(17),11,13-trien-15,16-olide (9), are isolated from the rhizomes of Hedychium coronarium. Compounds 2-4, 5 and 9 are isolated as mixtures of C-15, C-14 and C-16 epimers, respectively. Their structures are determined on the basis of their spectroscopic data. The epimeric mixtures of 2 and 3 have not been reported before. Some of them were evaluated for their cytotoxicity.     

Supramolecular structure of self-assembled synthetic zinc-13(1)-oxo-chlorins possessing a primary, secondary or tertiary alcoholic 3(1)-hydroxyl group: visible spectroscopic and molecular modeling studies

Zinc-chlorin 3 (see Fig. 2 in text) possessing a tertiary 3(1)-hydroxyl group and a 13-keto group was synthesized as a model for the antenna chlorophylls of green bacteria. Self-aggregation of 3 in nonpolar organic media was examined and compared to 1 and 2 possessing a primary and secondary 3(1)-hydroxyl group, respectively. Zinc-chlorin 3 self-aggregated in 1 vol% CH2Cl2-hexane to form oligomers and showed a red-shifted Qy maximum at 704 nm compared to the monomer (648 nm in CH2Cl2). This red-shift is larger than that of 2S (648-->697 nm) and comparable to that of 2R (648-->705 nm), but smaller than that of 1 (648-->740 nm), indicating that while a single 3(1)-methyl group (prim-OH-->sec-OH) suppressed close and/or higher aggregation, the additional 3(1)-methyl group (sec-OH-->tert-OH) did not further suppress aggregation. The relative stability of the aggregates was in the order 1 > 2R-3 > 2S as determined by visible spectral analyses. Molecular modeling calculations on dodecamers of zinc-chlorins 1, 2R and 3 gave similar well-ordered energy-minimized structures, while 1 stacked more tightly than 2R and 3. In contrast, 2S gave a relatively disordered (twisted) structure. The calculated dodecameric structures could explain the visible spectral data of 1-3 in nonpolar organic media.     

13C NMR spectral characterization of epimeric rotenone and some related tetrahydrobenzopyranofurobenzopyranones

The ¹³C nuclear magnetic resonance (nmr) spectra of epimers of rotenone and four 12a-hydroxy-analogues were examined to determine the stereochemical effect of the B/C ring fusion involving the 6a- and 12a-carbon centers. Chemical shift differences between the epimeric carbon resonances of cis- and trans-6a,12a-compounds were notably larger than those of diastereoisomers derived from the same B/C ring junction stereochemistry. Results of the spectral analysis have been useful for the quantification of mixtures of epimers and for the measurement of rates of epimerization and oxygenation.     

Diastereoselective self-aggregation of synthetic 3-(1-hydroxyethyl)-bacteriopyrochlophyll-a as a novel photosynthetic antenna model absorbing near the infrared regions

3-Deacetyl-3-(1-hydroxyethyl)bacteriopyrochlorophyll-a (1), 7,8-dihydrobacteriochlorophyll-d possessing 8-ethyl, 12-methyl and 17(4)-phytyl groups, was prepared by modifying naturally occurring bacteriochlorophyll-a. The synthetic 3(1)-epimers were separated by high-performance liquid chromotagraphy, and the absolute configuration at the 3(1)-position was determined by derivatization of 1 to a structurally determined chlorin. A dichloromethane solution of 3(1)R-1 or 3(1)S-1 was diluted with a 1000-fold volume of cyclohexane to give self-aggregation species absorbing light at a near-infrared (NIR) region (<910 nm). The resulting Qy maximum in 3(1)R-1 was 860 nm and redshifted by 2170 cm(-1) from the monomeric one, whereas epimeric 3(1)S-1 showed a less redshifted peak at ca 800 nm, with a small dimeric band around 740 nm. Such visible spectra indicated that 3(1)R/S-1 formed different supramolecular structures in the self-aggregates. In contrast, self-aggregation of the 7,8-dehydro-compound 2, bacteriochlorophyll-dP, found in natural antennas of photosynthetic green bacteria showed much smaller diastereomeric control. The self-aggregates of 3(1)R-1 absorbing light in the NIR region would be models of intrinsic membraneous light-harvesting complexes 1 in photosynthetic purple bacteria as well as extramembranous antennas in green bacteria.     

Synthesis and crystal structure of a novel chiral compound prepared from (-)-borneol as a natural chiral auxiliary

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阳离子表面活性剂存在下卟啉聚集的光谱研究

报导在阳离子表面活性剂溴化十六烷基三甲铵（CTMAB）存在下mcso-四（对-磺基苯基）卟啉（TPPS_4）发生聚集的电子吸收光谱、荧光光谱和共振光散射光谱特性．结果表明：CTMAB低于1．0×10~(－5)mol·L~(-1)时TPPS_4发生J-型聚集，形成一种交错卡迭式二聚体。在1．0×10~(－5)～1.0×10~(－4)mol·L~(－1)时，J-型聚集产物仍然存在，但TPPS_4的Soret蜂蓝移．如果CTMAB浓度高于1．0×10~（-4）mol·L~（-1），J-型聚集产物消失，出现游离碱卟啉的D_(2h)。吸收特征．相对于水介质，游离碱卟啉的Soret带在CTMAB胶束中红移．     

Facile synthesis of chlorophyll analog possessing a disulfide bond and formation of self-assembled monolayer on gold surface

A chlorophyll analog forming self-assembled monolayers (SAMs) on a gold surface was synthesized for the first time. 13(2)-(Demethoxycarbonyl)pheophorbide-a, which was converted from naturally occurring chlorophyll-a, was condensed with 2-hydroxyethyl disulfide to give a chlorin dyad linked by a disulfide bond. The chlorin analog was spontaneously immobilized on a gold substrate by soaking in an acetone solution of the dyad for 24 h. The resulting gold plate exhibited a visible absorption spectrum with about 420- and 675-nm maxima as the Soret and Qy peaks, respectively, indicating that chlorin pi-conjugates were modified on the gold substrate through Au-S bonding. Both visible absorption and fluorescence emission bands of the chlorin chromophores on the gold substrate were red-shifted compared with those of the synthesized chlorin dyad in a homogeneous acetone solution. The measured absorbance at the Soret maximum suggests that the chlorin chromophores on the gold plate were densely packed on a gold surface to form a SAM. Cathodic photocurrents were generated from SAMs of the chlorins on a gold substrate with irradiation of visible-lights above 400 nm. Photoinduced electron transfer from chlorins on the gold substrate to oxygen molecules in an electrolyte solution were attributed to the cathodic photocurrent generation.     

Dipole strengths of the Qy(0,0) bacteriochlorophyll c transition

The absorption spectra of bacteriochlorophyll (BChl) c solutions in two mixtures of two solvents (acetonitrile with pyridine and dimethylsulfoxide with methanol) exhibiting different refractive indices were measured and deconvoluted into Gaussian components. The refractive index of mixed solvents was changed by the change in the ratio of the volumes of the liquids used in the mixture. Using the Qy(0,0) band half widths and absorption coefficient, based on the simplified formula proposed by Knox, the dipole strengths of the Qy(0,0) BChl c transition for various values of solvent refractive index were calculated and compared with values given by Knox and Spring. For both investigated combinations of two liquids, the dependence of Qy(0,0) transition dipole strength of the BChl c on solvent refractive index was almost linear. The slopes of the lines obtained from the experimental absorption bands were different for two investigated solvent mixtures. More accurate linear dependence and similar slopes of lines for both solvent mixtures were obtained using half widths and absorption coefficients of the Gaussian components of Qy(0,0) transition. It is explained by the superposition of the contributions from other electronic and vibronic transitions of BChl c monomers or possibly also from transitions of the pigments involved in some complexes with solvent molecules in the absorption region investigated. The results show that the formula proposed by Knox can be successfully applied also for BChl c, after elimination of the overlapped contributions from the other transitions, by applying Gaussian analysis to select only contribution from Qy(0,0) pigment transition.     

Single site electronic spectroscopy of palladium chlorin in n-octane matrixes at 7K

The high resolution, single site emission and absorption spectra of palladium chlorin (PdC) in n-octane matrixes at 7K are reported. The emission and Q and Soret band absorption regions were investigated. The vibrational frequencies of the ground and the lowest energy pipi* excited states were determined from luminescence and excitation spectra, respectively. The emission from PdC was entirely phosphorescence. The emission and Qy region spectra of the complex are similar, having intense, narrow origin bands followed by relatively weak but orderly vibrational structure. The Qx region of this metal chlorin does not have a clear origin and exhibits complex vibrational structure which increases in intensity going to higher energy. In the Soret region of PdC there is only a single intense, broad band.     

Mixed Micellization of Dimeric (Gemini) Surfactants and Conventional Surfactants

The aqueous solutions of mixtures of various conventional surfactants and dimeric anionic and cationic surfactants have been investigated by electrical conductivity, spectrofluorometry, and time-resolved fluorescence quenching to determine the critical micelle concentrations and the micelle aggregation numbers in these mixtures. The following systems have been investigated: 12-2-12/DTAB, 12-2-12/C(12)E(6), 12-2-12/C(12)E(8), 12-3-12/C(12)E(8), Dim3/C(12)E(8), and Dim4/C(12)E(8) (12-2-12 and 12-3-12=dimethylene-1,2- and trimethylene-1,3-bis(dodecyldimethylammonium bromide), respectively; C(12)E(6) and C(12)E(8)=hexa- and octaethyleneglycol monododecylethers, respectively; Dim3 and Dim4=anionic dimeric surfactants of the disodium sulfonate type, Scheme 1; DTAB=dodecyltrimethylammonium bromide). For the sake of comparison the conventional surfactant mixtures DTAB/C(12)E(8) and SDS/C(12)E(8) (SDS=sodium dodecylsulfate) have also been investigated (reference systems). Synergism in micelle formation (presence of a minimum in the cmc vs composition plot) has been observed for the Dim4/C(12)E(8) mixture but not for other dimeric surfactant/nonionic surfactant mixtures investigated. The aggregation numbers of the mixed reference systems DTAB/C(12)E(8) and SDS/C(12)E(8) vary monotonously with composition from the value of the aggregation number of the pure C(12)E(8) to that of the pure ionic component. In contrast, the aggregation number of the dimeric surfactant/C(12)E(8) mixtures goes through a minimum at a low value of the dimeric surfactant mole fraction. This minimum does not appear to be correlated to the existence of synergism in micelle formation. The initial decrease of the aggregation number of the nonionic surfactant upon addition of ionic surfactant, up to a mole fraction of ionic surfactant of about 0.2 (in equivalent per total equivalent), depends little on the nature the surfactant, whether conventional or dimeric. The results also show that the microviscosity of the systems containing dimeric surfactants is larger than that of the reference systems. Copyright 2001 Academic Press.     

Counterion-dependent excitonic spectra of tetra(p-carboxyphenyl)porphyrin aggregates in acidic aqueous solution

Aggregates of the diacid form of tetra(p-carboxyphenyl)porphyrin (TCPP) are found to be stabilized in aqueous solution at low pH in the presence of poly(vinyl alcohol). At pH values in the range from about 1 to 4, a split Soret band is observed which is independent of counterion and tentatively assigned to a dimer species. As the pH is made lower than 1, the spectra evolve to reveal the presence of porphyrin aggregates. As in the case of the well-known aggregates of the related tetra(p-sulfonatophenyl)porphyrin (TSPP) diacid, the concentration of spectroscopically distinguishable aggregates increases with increasing ionic strength or decreasing pH. Unlike aggregates of TSPP, however, TCPP aggregates below pH 1 have visible absorption spectra which depend on the counterion, which is Cl(-) or NO(3)(-) in this study. In this work, we present visible absorption, light-scattering, and resonance Raman spectra of TCPP diacid in its monomer, dimer, and aggregated forms and attempt to understand the structural basis for counterion-dependent structure and excitonic coupling in the aggregates. Evidence is presented for intercalation of inorganic counterions between porphyrin molecules in the aggregate, an effect which to our knowledge has not been previously reported.     

A Quadruply Bridged Non-Offset Face-to-Face Porphyrin Dimer and Cross-Shaped Pentameric Porphyrin Tapes Based on 2,7,12,17-Tetrakis(pinacolatoboryl) NiII Porphyrin

2,7,12,17-Tetrakis(pinacolatoboryl) Ni^II porphyrin 5 Ni was synthesized in 75 % yield by Ir-catalyzed borylation of porphine followed by Ni^II metalation and has been demonstrated to be a useful synthon, giving 2,7,12,17-tetraaryated Ni^II porphyrins 6 a – d , peripherally octaarylated Ni^II porphyrins 8 a – d , quadruply bridged face-to-face non-offset Ni^II-porphyrin dimer 12 , and cross-shaped β-meso singly linked porphyrin pentamers and nonamers. Oxidation of cross-shaped β-meso singly linked porphyrin pentamers 14 Ni and 14 Zn gave fused pentameric tapes 15 Ni and 15 Zn . The structures of 12 , 14 Zn , and 15 Ni have been revealed by X-ray diffraction analysis. Optical separation of 12 has been accomplished, showing a bisignate coupling pattern for exciton-coupled blue-shifted Soret band. Pentameric porphyrin tape 15 Zn exhibits a red-shifted absorption band at 1156 nm and seven reversible redox waves.     

Effects of organic and aqueous solvents on the electronic absorption and fluorescence of chloroaluminum (III) tetrasulphonated naphthalocyanine

The effects of various solvents on the ground and excited states of chloroaluminum (III) tetrasulphonated naphthalocyanine (AlNcS(4)) were studied. Both the absorbance and fluorescence spectra were found to be influenced by the hydrogen bond donating ability of various solvents. As the hydrogen bond donating ability of the solvent increased, hypsochromic and bathochromic shifts in the absorbance and fluorescence spectra were observed in protic and aprotic solvents respectively. Plots of the absorbance and fluorescence maxima versus the E(T)(30) solvent parameter showed linear relationships in binary mixtures of protic-protic (methanol-H(2)O) and aprotic-protic (DMSO-H(2)O) solvents. Aggregation was indicated by a broad band in the ground state absorption spectra and a low quantum efficiency 0.04 relative to the efficiency observed in organic solvents. A face-to-face conformation of the monomeric subunits of the dimer is suggested due to the red-shifted absorbance band. The acid-base properties of the dye were studied and were indicative of a multi-step process. In acidic conditions (pH 1), protonation of the bridging nitrogen atoms was identified by a broad band appearing red-shifted to those obtained at higher pH values. Under slightly acidic conditions a pKa value of 6.7 was determined for one of the meso-nitrogen. In alkaline conditions a pKa of 11.5 was determined for another meso-nitrogen and a second fluorescence band emerged at 804 nm, red-shifted to the emission maxima.     

SANS studies of the effects of surfactant head group on aggregation properties in water/glycol and pure glycol systems

Aggregation in mixed water-glycol and pure glycol solvents has been investigated with four related surfactants, bearing common C12 tails: anionic, sodium dodecylsulfate (SDS); cationic, dodecyltrimethylammonium bromide (C12TAB); zwitterionic C12-amidopropyldimethylamine betaine (betaine) and nonionic, octaethyleneglycol monododecyl ether (C12E8). The solvent media were water, water/ethylene glycol, and water/propylene glycol mixtures, as well as pure ethylene glycol (EG) and propylene glycol (PG), spanning relative dielectrics epsilon(r) from 79 to 30. Results from small-angle neutron scattering (SANS) experiments, employing deuterated solvents, were consistent with the presence of ellipsoidal, or cylindrical micelles, depending on solvent and surfactant type. In pure EG and PG solvents the ionic and zwitterionic surfactants exhibit only weak aggregation, with much smaller micelles than normally found in water. However, interestingly, pure EG is identified as a solvent in which nonionic C12E8 aggregates strongly, mirroring the behavior in water. In contrast when the solvent is changed to PG (epsilonr=30) aggregation of C12E8 is only minimal. Hence, aggregation is shown to be strongly dependent on surfactant type and identity of the glycol solvent.     

Determination of (15R)- and (15S)-15-methylprostaglandin E2 in human plasma with picogram per milliliter sensitivity by column-switching high-performance liquid chromatography

(15R)-15-Methylprostaglandin E2 (PGE2) is a pro-drug under evaluation for the treatment of acute upper gastrointestinal hemorrhage and gastrointestinal cytoprotection. It is converted in acid (e.g., gastric fluid) to its active 15S epimer. Both epimers are found in human plasma at low pg/ml levels following oral dosing. A high-performance liquid chromatographic (HPLC) method was developed for the simultaneous analysis of (15R)- and (15S)-15-methyl-PGE2 in human plasma. The method combined off-line solid-phase extraction and reversed-phase HPLC clean-up with panacyl bromide derivatization and subsequent analysis using a heteromodal column-switching technique. Assay linearity was demonstrated over a range of 10-200 pg/ml for both 15-methyl-PGE2 epimers (r greater than or equal to 0.995). There were no significant inter-day differences in assay results for either epimer at 50 and 25 pg/ml (p greater than 0.05), with pooled estimates of precision at these levels producing relative standard deviations of less than or equal to 8% and less than or equal to 12%, respectively. The method quantitation limit (signal-to-noise ratio 5:1) for both epimers was 10 pg/ml when processing 3 ml of plasma. The analysis procedure was shown to be useful for quantifying at or below 10% of the (15R)-15-methyl-PGE2 maximum plasma concentration following a 50-micrograms oral dose in three human volunteers. For the same three subjects, however, the plasma concentration of (15S)-15-methyl-PGE2 did not exceed the quantitation limit of 10 pg/ml.     

Mixed micelle formation among anionic gemini surfactant (212) and its monomer (SDMA) with conventional surfactants (C12E5 and C12E8) in brine solution at pH 11

The micellization of anionic gemini surfactant, N,N'-ethylene(bis(sodium N-dodecanoyl-beta-alaninate)) (212), and its monomer, N-dodecanoyl-N-methyl alaninate (SDMA), and polyethoxylated nonionic surfactants, C(12)E(5) and C(12)E(8), has been studied tensiometrically in pure and mixed states in an aqueous solution of 0.1 M NaCl at pH 11 to determine physicochemical properties such as critical micellar concentration (cmc), surface tension at the cmc (gamma(cmc)), maximum surface excess (Gamma(max)) and minimum area per surfactant molecule at the air/water interface (A(min)). The theories of Rosen, Rubingh, Motomura, Maeda, and Nagarajan have been applied to investigate the interaction between those surfactants at the interface and in the micellar solution, the composition of the aggregates formed, the theoretical cmc in pure and mixed states, and the structural parameters as proposed by Tanford and Israelachvili. Various thermodynamic parameters (free energy of micellization and interfacial adsorption) have been calculated with the help of regular solution theory and the pseudophase model for micellization.     

C-Alkylation of Peptides Containing Aminomalonate and (Amino)(cyano)acetate Residues

N-Acetyl-, N-[(tert-butoxy)carbonyl](Boc)-, and N-[(benzyloxy)carbonyl](Z)-protected tri-, penta-, and heptapeptide methyl esters, 1 – 8 , with a central aminomalonate (Ama) (allyl, methyl, benzyl, or tert-butyl) or (amino)(cyano)acetate (Aca) residue have been prepared by conventional techniques (Schemes 4 – 6). The new peptides with acidic backbone-bound CH groups can be C-alkylated with primary alkyl, allyl, and benzyl halides, under mildly basic conditions (1 equiv. MeONa or t-BuOK in THF); also, they can be added to Michael acceptors such as acrylates, acrylonitrile, methyl vinyl ketone, or nitrostyrene (catalytic amounts of alkoxide bases in THF) (Schemes 7 – 16). In most cases, the products, 48 – 100 , are formed in excellent yields (average of 77%); one of the epimeric products prevails (2 : 1 to > 20 : 1), and the epimers have been separated, isolated in pure form, and fully characterized (without configurational assignments); addition of the co-solvent 3,4,5,6-tetrahydro-1,3-dimethylpyrimidin-2(1H)-one (DMPU) or of LiBr may improve or even reverse the ratio of epimeric products formed; the heptapeptide derivative 8 had to be solubilized for alkylations in THF by the addition of 30 equiv. of LiBr. Cleavage of the Ama groups (benzyl with H₂/Pd-C, t-Bu with HCl/Et₂O) gave carboxylate derivatives which are actually peptides containing the alkylated aminomalonic acid, the lower homolog of aspartic acid, as residue in the central position. These acids are quite resistant to decarboxylation which had to be achieved by heating at reflux in THF in the presence of 2 equiv. of LiBr and of catalytic amounts of pyridine (Schemes 17 and 18). A one-step removal of the allyl aminomalonate group is possible with Pd/PPh₃/formate (Scheme 19). The resulting peptides, 101 – 115 , were formed as separable 1 : 1 mixtures of two epimers. The CN group of the alkylated Aca residue can be removed reductively (Na/NH₃; Scheme 20). The value of the new method is compared with that of existing methods of peptide-backbone modification.     

Excited-state absorption and ultrafast relaxation dynamics of porphyrin, diprotonated porphyrin, and tetraoxaporphyrin dication

The relaxation dynamics of unsubstituted porphyrin (H2P), diprotonated porphyrin (H4P2+), and tetraoxaporphyrin dication (TOxP2+) has been investigated in the femtosecond-nanosecond time domain upon photoexcitation in the Soret band with pulses of femtosecond duration. By probing with spectrally broad femtosecond pulses, we have observed transient absorption spectra at delay times up to 1.5 ns. The kinetic profiles corresponding with the band maxima due to excited-state absorption have been determined for the three species. Four components of the relaxation process are distinguished for H2P: the unresolvably short B --> Qy internal conversion is followed by the Qy --> Qx process, vibrational relaxation, and thermalization in the Qx state with time constant approximately 150 fs, 1.8 ps, and 24.9 ps, respectively. Going from H2P to TOxP2+, two processes are resolved, i.e., B --> Q internal conversion and thermal equilibration in the Q state. The B --> Q time constant has been determined to be 25 ps. The large difference with respect to the B --> Qy time constant of H2P has been related to the increased energy gap between the coupled states, 9370 cm-1 in TOxP2+ vs 6100 cm-1 in H2P. The relaxation dynamics of H4P2+ has a first ultrafast component of approximately 300 fs assigned as internal conversion between the B (or Soret) state and charge-transfer (CT) states of the H4P2+ complex with two trifluoroacetate counterions. This process is followed by internal CT --> Q conversion (time constant 9 ps) and thermalization in the Q state (time constant 22 ps).     

氨基吡啶修饰碳纳米管的制备及其与辣根过氧化酶的相互作用

用重铬酸钾氧化法获得了表面羧基化的碳纳米管(MWCNT-COOH), 进一步通过酰胺化反应合成了2-氨基吡啶修饰的碳纳米管(MWCNT-AP). 利用傅里叶变换红外(FT-IR)光谱、核磁共振氢谱(¹H NMR)、X射线光电子能谱(XPS)等对合成的碳纳米管进行了表征. 透射电镜(TEM)结果表明MWCNT-COOH在乙醇等极性溶剂中易于簇集, 而MWCNT-AP 溶液具有良好的分散性和稳定性. 辣根过氧化酶(HRP)可通过物理作用吸附于MWCNT-AP 和MWCNT-COOH表面, 负载量分别为187.5 和153.0 μg·mg^-1. HRP被吸附后, 其Soret 带明显红移, 说明HRP 与MWCNT-AP 或MWCNT-COOH 的结合位点位于血红素辅基的附近. 圆二色谱结果表明MWCNT-AP 对HRP的二级结构也有一定影响. 酶动力学实验结果表明MWCNT-AP 能有效地吸附HRP及其底物3,3',5,5'-四甲基联苯胺(TMB), 并使HRP的酶催化反应最大速率(V_max)显著提高.